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Here, we present a multi-season study of ice-nucleating particles (INPs) active via the immersion freezing mechanism, which took place in north-central Argentina, a worldwide hotspot for mesoscale convective storms. INPs were measured untreated, after heating to 95°C, and after hydrogen peroxide digestion. No seasonal cycle of INP concentrations was observed. Heat labile INPs, which we define as “biological” herein, dominated the population active at −5 to −20°C, while non-heat-labile organic INPs (decomposed by peroxide) dominated at lower temperatures, from −20 to −28°C. Inorganic INPs (remaining after peroxide digestion), were minor contributors to the overall INP activity. Biological INP concentration active around −12°C peaked during rain events and under high relative humidity, reflecting emission mechanisms independent of the background aerosol concentration. The ratio of non-heat-labile organic and inorganic INPs was generally constant, suggesting they originated from the same source, presumably from regional arable topsoil based on air mass histories. Single particle mass spectrometry showed that soil particles aerosolized from a regionally common agricultural topsoil contained known mineral INP sources (K-feldspar and illite) as well as a significant organic component. The INP activity observed in this study correlates well with agricultural soil INP activities from this and other regions of the world, suggesting that the observed INP spectra might be typical of many arable landscapes. These results demonstrate the strong influence of regional continental landscapes, emitting INPs of types that are not yet well represented in global models., Journal of Geophysical Research: Atmospheres, 126 (23), ISSN:0148-0227, ISSN:2169-897X

Volcanic ash (VA) from explosive eruptions contributes to aerosol loadings in the atmosphere. Aside from the negative impact of VA on air quality and aviation, these particles can alter the optical and microphysical properties of clouds by triggering ice formation, thereby influencing precipitation and climate. Depending on the volcano and eruption style, VA displays a wide range of different physical, chemical, and mineralogical properties. Here, we present a unique data set on the ice nucleation activity of 15 VA samples obtained from different volcanoes worldwide. The ice nucleation activities of these samples were studied in the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud simulation chamber as well as with the Ice Nucleation Spectrometer of the Karlsruhe Institute of Technology (INSEKT). All VA particles nucleated ice in the immersion freezing mode from 263 to 238K with ice nucleation active site (INAS) densities ranging from ∼105 to 1011 m−2, respectively. The variabilities observed among the VA samples, at any given temperature, range over 3.5 orders of magnitude. The ice‐nucleating abilities of VA samples correlate to varying degrees with their bulk pyroxene and plagioclase contents as a function of temperature. We combined our new data set with existing literature data to develop an improved ice nucleation parameterization for natural VA in the immersion freezing mode. This should be useful for modeling the impact of VA on clouds., Plain Language Summary: Volcanic ash particles, which are generated during volcanic eruptions, can initiate ice formation in clouds. The clouds formed by these volcanic ash particles can influence precipitation, and in turn, weather and climate. In our study, we investigated the ability with which volcanic ash particles form ice in clouds. We performed our study in a state‐of‐the‐art aerosol and cloud simulation chamber and on a cold‐stage instrument. The findings show that volcanic ash particles can form ice as effectively as mineral dust particles or their components. These results will help scientists to have a better understanding of the impact of volcanic ash particles on clouds., Key Points: The ice‐nucleating ability of natural volcanic ash particles in the immersion freezing mode can vary by 3.5 orders of magnitude. Ice‐nucleating properties of volcanic ash particles correlate to varying degrees with their pyroxene and plagioclase contents. The temperature‐dependent immersion freezing ability of volcanic ash is approximated with an exponential fit line., Alexander von Humboldt‐Stiftung (Humboldt‐Stiftung) http://dx.doi.org/10.13039/100005156, Marie Skłodowska‐Curie Actions, ERC 2018 ADG, Deutsche Forschungsgemeinschaft (DFG) http://dx.doi.org/10.13039/501100001659, Helmholtz Association of German Research Centres, EUROCHAMP 2020 Infrastructure Activity

This study presents a comprehensive investigation of ice-nucleating particles (INPs) in the surface materials and aerosol particles from U.S. cattle feeding facilities. Using a modern suite of online and offline aerosol particle characterization instruments, we conducted a three-year field survey (2016–2019), Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber experiments, and ice crystal residual (ICR) analyses for the feedlot sample. Our results showed unique supermicron size dominance in the feedlot INPs with a high concentration of INPs (several hundred and thousand INPs L−1 at −20 °C and −25 °C, respectively). Thus, agricultural fields, especially animal feeding facilities, represent important INP sources if these particles rise to sufficient height in the atmosphere. New data on the ice nucleation (IN) properties of agricultural dust at heterogeneous freezing temperatures (Ts > −29 °C) were generated, providing statistical context. Overall, we successfully characterized physical, chemical, and biological properties of aerosol particles found at a cattle feedlot, thereby finding their unique heat-tolerant nature. The relationship between these measured properties and atmospheric IN parameterization relevant to mixed-phase clouds is discussed. Our INP parameterization and ICR characterization are meaningful for improved understanding of INP emission and cloud microphysical processes in the supermicron-particle laden region. These unique INPs may directly influence the lifetime of supercooled clouds in a unique manner for this region. An application of our IN parameterization is crucial to explore INP relations to supercooled cloud properties over such a predominant agricultural area.

We present our field results of ice-nucleating particle (INP) measurements from the commercialized version of the Portable Ice Nucleation Experiment (PINE) chamber from two different campaigns. Our first field campaign, TxTEST, was conducted at West Texas A&M University (July–August 2019), and the other campaign, ExINP-SGP, was held at the Atmospheric Radiation Measurement (ARM) Southern Great Plains (SGP) site (October–November 2019). In both campaigns, the PINE made semi-autonomous INP measurements at a high-time-resolution of 8 min for individual expansions with continuous temperature scans from −5 to −35 °C in 90 min. The PINE instrument was set to have a minimum detection capability of ~0.3 INPs per liter of air. To complement our online PINE measurements, polycarbonate filter impactor and liquid impinger samples were also collected next to the PINE. Offline droplet-freezing assays were later conducted from the filter and impinger samples for the immersion freezing mode. Our preliminary results suggested that the immersion freezing mode was the dominant ice-nucleation mechanism at the SGP site compared to the deposition mode. We did not find any statistical correlation between cloud condensation nuclei (CCN) and INP concentration during our ExINP-SGP period, suggesting that CCN activation is not a significant prerequisite for ice nucleation at the SGP site. In addition, we analyzed the relationship between various aerosol particle size ranges and INP abundance. At SGP, we found an increase in INPs with the super-micron particles, especially for diameters >2 μm across the entire heterogeneous freezing temperature range examined by PINE. Lastly, we computed a variety of INP parameters, such as, ice nucleation active surface site density, water activity-based freezing, and cumulative INP per liter of air, representing the ambient INPs in the SGP. Our field campaign results demonstrated the PINE’s ability to make remote INP measurements, promising future long-term operations including at isolated locations.

In recent years, sea spray and the biological material it contains has received increased attention as a source of ice nucleating particles (INPs). Such INPs may play a role in remote marine regions, where other sources of INPs are scarce or absent. Marine aerosol is of diverse nature, so identifying sources of INPs is challenging. One fraction of marine bioaerosol, phytoplankton and their exudates, has been a particular focus of marine INP research. In our study we attempt to address three main questions. Firstly, we compare the ice nucleating ability of two common phytoplankton species with Arctic seawater microlayer samples using the same instrumentation to see if these phytoplankton species produce ice nucleating material with sufficient activity to account for the ice nucleation observed in Arctic microlayer samples. We present first measurements of the ice nucleating ability of two predominant phytoplankton species, Melosira arctica, a common Arctic diatom species and Skeletonema marinoi, a ubiquitous diatom species across oceans worldwide. To determine the potential effect of nutrient conditions and characteristics of the algal culture, such as the amount of organic carbon associated with algal cells, on the ice nucleation activity, the Skeletonema marinoi was grown under different nutrient regimes. From comparison of the ice nucleation data of the algal cultures to those obtained from a range of sea surface microlayer (SML) samples obtained during three different field expeditions to the Arctic (ACCACIA, NETCARE, ASCOS) we found that although these diatoms do produce ice nucleating material, they were not as ice active as the investigated microlayer samples. Secondly, to improve our understanding of local Arctic marine sources as atmospheric INP we applied several aerosolisation techniques to analyse the ice nucleating ability of aerosolised microlayer and algae samples. The aerosols were generated either by direct nebulisation of the undiluted bulk solutions, or by the addition of the samples to a sea spray simulation chamber filled with artificial seawater. The latter method generates aerosol particles using a plunging jet to mimic the process of oceanic wave-breaking. We observed that the aerosols produced using this approach can be ice active indicating that the ice nucleating material in seawater can indeed transfer to the aerosol phase. Thirdly, we attempted to measure ice nucleation activity across the entire temperature range relevant for mixed-phase clouds using a suite of ice nucleation measurement techniques- an expansion cloud chamber, a continuous flow diffusion chamber, and a cold stage. In order to compare the measurements made using the different instruments, we have normalised the data in relation to the mass of salt present in the nascent sea spray aerosol. At temperatures above 248 K some of the SML samples were very effective at nucleating ice, but there was substantial variability between the different samples. In contrast, there was much less variability between samples below 248 K.

In situ measurements of the composition of heterogeneous cirrus ice cloud residuals have indicated a substantial contribution of sea salt in sampling regions above the ocean. We have investigated the heterogeneous ice nucleation ability of sodium chloride (NaCl) and sea salt aerosol (SSA) particles at cirrus cloud temperatures between 235 and 200 K in the Aerosol Interaction and Dynamics in the Atmosphere aerosol and cloud chamber. Effloresced NaCl particles were found to act as ice nucleating particles in the deposition nucleation mode at temperatures below about 225 K, with freezing onsets in terms of the ice saturation ratio, Sice, between 1.28 and 1.40. Above 225 K, the crystalline NaCl particles deliquesced and nucleated ice homogeneously. The heterogeneous ice nucleation efficiency was rather similar for the two crystalline forms of NaCl (anhydrous NaCl and NaCl dihydrate). Mixed-phase (solid/liquid) SSA particles were found to act as ice nucleating particles in the immersion freezing mode at temperatures below about 220 K, with freezing onsets in terms of Sice between 1.24 and 1.42. Above 220 K, the SSA particles fully deliquesced and nucleated ice homogeneously. Ice nucleation active surface site densities of the SSA particles were found to be in the range between 1.0 · 1010 and 1.0 · 1011 m−2 at T

The ice nucleation ability of α-pinene secondary organic aerosol (SOA) particles was investigated at temperatures between 253 and 205 K in the Aerosol Interaction and Dynamics in the Atmosphere cloud simulation chamber. Pristine SOA particles were nucleated and grown from pure gas precursors and then subjected to repeated expansion cooling cycles to compare their intrinsic ice nucleation ability during the first nucleation event with that observed after ice cloud processing. The unprocessed α-pinene SOA particles were found to be inefficient ice-nucleating particles at cirrus temperatures, with nucleation onsets (for an activated fraction of 0.1%) as high as for the homogeneous freezing of aqueous solution droplets. Ice cloud processing at temperatures below 235 K only marginally improved the particles' ice nucleation ability and did not significantly alter their morphology. In contrast, the particles' morphology and ice nucleation ability was substantially modified upon ice cloud processing in a simulated convective cloud system, where the α-pinene SOA particles were first activated to supercooled cloud droplets and then froze homogeneously at about 235 K. As evidenced by electron microscopy, the α-pinene SOA particles adopted a highly porous morphology during such a freeze-drying cycle. When probing the freeze-dried particles in succeeding expansion cooling runs in the mixed-phase cloud regime up to 253 K, the increase in relative humidity led to a collapse of the porous structure. Heterogeneous ice formation was observed after the droplet activation of the collapsed, freeze-dried SOA particles, presumably caused by ice remnants in the highly viscous material or the larger surface area of the particles.

Based on results of 11 yr of heterogeneous ice nucleation experiments at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber in Karlsruhe, Germany, a new empirical parameterization framework for heterogeneous ice nucleation was developed. The framework currently includes desert dust and soot aerosol and quantifies the ice nucleation efficiency in terms of the ice nucleation active surface site (INAS) approach. The immersion freezing INAS densities nS of all desert dust experiments follow an exponential fit as a function of temperature, well in agreement with an earlier analysis of AIDA experiments. The deposition nucleation nS isolines for desert dust follow u-shaped curves in the ice saturation ratio–temperature (Si–T) diagram at temperatures below about 240 K. The negative slope of these isolines toward lower temperatures may be explained by classical nucleation theory (CNT), whereas the behavior toward higher temperatures may be caused by a pore condensation and freezing mechanism. The deposition nucleation measured for soot at temperatures below about 240 K also follows u-shaped isolines with a shift toward higher Si for soot with higher organic carbon content. For immersion freezing of soot aerosol, only upper limits for nS were determined and used to rescale an existing parameterization line. The new parameterization framework is compared to a CNT-based parameterization and an empirical framework as used in models. The comparison shows large differences in shape and magnitude of the nS isolines especially for deposition nucleation. For the application in models, implementation of this new framework is simple compared to that of other expressions.

Glaciation in mixed-phase clouds predominantly occurs through the immersion-freezing mode where ice-nucleating particles (INPs) immersed within supercooled droplets induce the nucleation of ice. Model representations of this process currently are a large source of uncertainty in simulating cloud radiative properties, so to constrain these estimates, continuous-flow diffusion chamber (CFDC)-style INP devices are commonly used to assess the immersion-freezing efficiencies of INPs. This study explored a new approach to operating such an ice chamber that provides maximum activation of particles without droplet breakthrough and correction factor ambiguity to obtain high-quality INP measurements in a manner that previously had not been demonstrated to be possible. The conditioning section of the chamber was maintained at −20 ∘C and water relative humidity (RHw) conditions of 113 % to maximize the droplet activation, and the droplets were supercooled with an independently temperature-controlled nucleation section at a steady cooling rate (0.5 ∘C min−1) to induce the freezing of droplets and evaporation of unfrozen droplets. The performance of the modified compact ice chamber (MCIC) was evaluated using four INP species: K-feldspar, illite-NX, Argentinian soil dust, and airborne soil dusts from an arable region that had shown ice nucleation over a wide span of supercooled temperatures. Dry-dispersed and size-selected K-feldspar particles were generated in the laboratory. Illite-NX and soil dust particles were sampled during the second phase of the Fifth International Ice Nucleation Workshop (FIN-02) campaign, and airborne soil dust particles were sampled from an ambient aerosol inlet. The measured ice nucleation efficiencies of model aerosols that had a surface active site density (ns) metric were higher but mostly agreed within 1 order of magnitude compared to results reported in the literature.

The rise of ammonia emissions in Asia is predicted to increase radiative cooling and air pollution by forming ammonium nitrate particles in the lower troposphere. There is, however, a severe lack of knowledge about ammonia and ammoniated aerosol particles in the upper troposphere and their possible effects on the formation of clouds. Here we employ satellite observations and high-altitude aircraft measurements, combined with atmospheric trajectory simulations and cloud-chamber experiments, to demonstrate the presence of ammonium nitrate particles and also track the source of the ammonia that forms into the particles. We found that during the Asian monsoon period, solid ammonium nitrate particles are surprisingly ubiquitous in the upper troposphere from the Eastern Mediterranean to the Western Pacific—even as early as in 1997. We show that this ammonium nitrate aerosol layer is fed by convection that transports large amounts of ammonia from surface sources into the upper troposphere. Impurities of ammonium sulfate allow the crystallization of ammonium nitrate even in the conditions, such as a high relative humidity, that prevail in the upper troposphere. Solid ammonium nitrate particles in the upper troposphere play a hitherto neglected role in ice cloud formation and aerosol indirect radiative forcing. Solid ammonium nitrate particles are formed in the upper troposphere during the Asian monsoons, which bring large amounts of ground ammonia to this altitude, according to integrated analyses of measurements on ammoniated aerosol, together with model simulations.

In this study, novel wood combustion aging experiments performed at different temperatures (263 and 288 K) in a ∼ 7 m3 smog chamber were modelled using a hybrid volatility basis set (VBS) box model, representing the emission partitioning and their oxidation against OH. We combine aerosol–chemistry box-model simulations with unprecedented measurements of non-traditional volatile organic compounds (NTVOCs) from a high-resolution proton transfer reaction mass spectrometer (PTR-MS) and with organic aerosol measurements from an aerosol mass spectrometer (AMS). Due to this, we are able to observationally constrain the amounts of different NTVOC aerosol precursors (in the model) relative to low volatility and semi-volatile primary organic material (OMsv), which is partitioned based on current published volatility distribution data. By comparing the NTVOC ∕ OMsv ratios at different temperatures, we determine the enthalpies of vaporization of primary biomass-burning organic aerosols. Further, the developed model allows for evaluating the evolution of oxidation products of the semi-volatile and volatile precursors with aging. More than 30 000 box-model simulations were performed to retrieve the combination of parameters that best fit the observed organic aerosol mass and O : C ratios. The parameters investigated include the NTVOC reaction rates and yields as well as enthalpies of vaporization and the O : C of secondary organic aerosol surrogates. Our results suggest an average ratio of NTVOCs to the sum of non-volatile and semi-volatile organic compounds of ∼ 4.75. The mass yields of these compounds determined for a wide range of atmospherically relevant temperatures and organic aerosol (OA) concentrations were predicted to vary between 8 and 30 % after 5 h of continuous aging. Based on the reaction scheme used, reaction rates of the NTVOC mixture range from 3.0 × 10−11 to 4. 0 × 10−11 cm3 molec−1 s−1. The average enthalpy of vaporization of secondary organic aerosol (SOA) surrogates was determined to be between 55 000 and 35 000 J mol−1, which implies a yield increase of 0.03–0.06 % K−1 with decreasing temperature. The improved VBS scheme is suitable for implementation into chemical transport models to predict the burden and oxidation state of primary and secondary biomass-burning aerosols.

Biological particles, including bacteria and bacterial fragments, have been of much interest due to the special ability of some to nucleate ice at modestly supercooled temperatures. This paper presents results from a recent study conducted on two strains of cultivated bacteria which suggest that bacterial fragments mixed with agar, and not whole bacterial cells, serve as cloud condensation nuclei (CCN). Due to the absence of whole bacteria cells in droplets, they are unable to serve as ice nucleating particles (INPs) in the immersion mode under the experimental conditions. Experiments were conducted at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber at the Karlsruhe Institute of Technology (KIT) by injecting bacteria-containing aerosol samples into the cloud chamber and inducing cloud formation by expansion over a temperature range of −5 to −12 ∘C. Cloud droplets and ice crystals were sampled through a pumped counterflow virtual impactor inlet (PCVI) and their residuals were characterized with a single particle mass spectrometer (miniSPLAT). The size distribution of the overall aerosol was bimodal, with a large particle mode composed of intact bacteria and a mode of smaller particles composed of bacterial fragments mixed with agar that were present in higher concentrations. Results from three expansions with two bacterial strains indicate that the cloud droplet residuals had virtually the same size distribution as the smaller particle size mode and had mass spectra that closely matched those of bacterial fragments mixed with agar. The characterization of ice residuals that were sampled through an ice-selecting PCVI (IS-PCVI) also shows that the same particles that activate to form cloud droplets, bacteria fragments mixed with agar, were the only particle type observed in ice residuals. These results indicate that the unavoidable presence of agar or other growth media in all laboratory studies conducted on cultivated bacteria can greatly affect the results and needs to be considered when interpreting CCN and IN activation data.

This study reports on heterogeneous ice nucleation efficiency of immersed oxalic and succinic acid crystals in the temperature range from 245 to 215 K, as investigated with expansion cooling experiments using suspended particles. In contrast to previous laboratory work with emulsified solution droplets where the precipitation of solid inclusions required a preceding freezing/evaporation cycle, we show that immersed solids readily form by homogeneous crystallization within aqueous solution droplets of multicomponent organic mixtures, which have noneutonic compositions with an excess of oxalic or succinic acid. Whereas succinic acid crystals did not act as heterogeneous ice nuclei, immersion freezing by oxalic acid dihydrate crystals led to a reduction of the ice saturation ratio at freezing onset by 0.066–0.072 compared to homogeneous freezing, which is by a factor of 2 higher than previously reported laboratory data. These observations emphasize the importance of oxalic acid in heterogeneous ice nucleation.

The mass spectral signatures of airborne bacteria were measured and analyzed in cloud simulation experiments at the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) facility. Suspensions of cultured cells in pure water were sprayed into the aerosol and cloud chambers forming an aerosol which consisted of intact cells, cell fragments and residual particles from the agar medium in which the bacteria were cultured. The aerosol particles were analyzed with a high-resolution time-of-flight aerosol mass spectrometer equipped with a newly developed PM2.5 aerodynamic lens. Positive matrix factorization (PMF) using the multilinear engine (ME-2) source apportionment was applied to deconvolve the bacteria and agar mass spectral signatures. The bacteria mass fraction contributed between 75 and 95% depending on the aerosol generation, with the remaining mass attributed to agar. We present mass spectra of Pseudomonas syringae and Pseudomonas fluorescens bacteria typical for ice-nucleation active bacteria in the atmosphere to facilitate the distinction of airborne bacteria from other constituents in ambient aerosol, e.g. by PMF/ME-2 source apportionment analyses. Nitrogen-containing ions were the most salient feature of the bacteria mass spectra, and a combination of C4H8N+ (m/z 70) and C5H12N+ (m/z 86) may be used as marker ions. Copyright © 2015 John Wiley & Sons, Ltd.

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an intercomparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques. Within the framework of INUIT (Ice Nuclei Research Unit), we distributed an illite-rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. A total of 17 measurement methods were involved in the data intercomparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while 10 other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing data set was evaluated using the ice nucleation active surface-site density, ns, to develop a representative ns(T) spectrum that spans a wide temperature range (−37 °C < T < −11 °C) and covers 9 orders of magnitude in ns. In general, the 17 immersion freezing measurement techniques deviate, within a range of about 8 °C in terms of temperature, by 3 orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency expressed in ns of illite NX particles is relatively independent of droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature dependence and weak time and size dependence of the immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns(T) spectra and identified a section with a steep slope between −20 and −27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below −27 °C. While the agreement between different instruments was reasonable below ~ −27 °C, there seemed to be a different trend in the temperature-dependent ice nucleation activity from the suspension and dry-dispersed particle measurements for this mineral dust, in particular at higher temperatures. For instance, the ice nucleation activity expressed in ns was smaller for the average of the wet suspended samples and higher for the average of the dry-dispersed aerosol samples between about −27 and −18 °C. Only instruments making measurements with wet suspended samples were able to measure ice nucleation above −18 °C. A possible explanation for the deviation between −27 and −18 °C is discussed. Multiple exponential distribution fits in both linear and log space for both specific surface area-based ns(T) and geometric surface area-based ns(T) are provided. These new fits, constrained by using identical reference samples, will help to compare IN measurement methods that are not included in the present study and IN data from future IN instruments.

Cirrus clouds and their impact on the Earth's radiative budget are subjects of current research. The processes governing the growth of cirrus ice particles are central to the radiative properties of cirrus clouds. At temperatures relevant to cirrus clouds, the growth of ice crystals smaller than a few microns in size is strongly influenced by the accommodation coefficient of water molecules on ice, αice, making this parameter relevant for cirrus cloud modeling. However, the experimentally determined magnitude of αice for cirrus temperatures is afflicted with uncertainties of almost three orders of magnitude, and values for αice derived from cirrus cloud data lack significance so far. This has motivated dedicated experiments at the cloud chamber AIDA (Aerosol Interactions and Dynamics in the Atmosphere) to determine αice in the cirrus-relevant temperature interval between 190 K and 235 K under realistic cirrus ice particle growth conditions. The experimental data sets have been evaluated independently with two model approaches: the first relying on the newly developed model SIGMA (Simple Ice Growth Model for determining Alpha), the second one on an established model, ACPIM (Aerosol-Cloud-Precipitation Interaction Model). Within both approaches a careful uncertainty analysis of the obtained αice values has been carried out for each AIDA experiment. The results show no significant dependence of αice on temperature between 190 K and 235 K. In addition, we find no evidence for a dependence of αice on ice particle size or on water vapor supersaturation for ice particles smaller than 20 μm and supersaturations of up to 70%. The temperature-averaged and combined result from both models is αice = 0.7−0.5+0.3, which implies that αice may only exert a minor impact on cirrus clouds and their characteristics when compared to the assumption of αice =1. Impact on prior calculations of cirrus cloud properties, e.g., in climate models, with αice typically chosen in the range 0.2–1 is thus expected to be negligible. In any case, we provide a well-constrained αice which future cirrus model studies can rely on.

The hygroscopic growth and droplet activation of uncoated soot particles and such coated with succinic acid and sulfuric acid were investigated during the IN-11 campaign at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) facility. A GFG-1000 soot generator applying either nitrogen or argon as carrier gas and a miniCAST soot generator were utilized to generate soot particles. Different organic carbon (OC) to black carbon (BC) ratios were adjusted for the CAST-soot by varying the fuel to air ratio. The hygroscopic growth was investigated by means of the mobile Leipzig Aerosol Cloud Interaction Simulator (LACIS-mobile) and two different Hygroscopicity Tandem Differential Mobility Analyzers (HTDMA, VHTDMA). Two Cloud Condensation Nucleus Counter (CCNC) were applied to measure the activation of the particles. For the untreated soot particles neither hygroscopic growth nor activation was observed at a supersaturation of 1%, with exception of a partial activation of GFG-soot generated with argon as carrier gas. Coatings of succinic acid lead to a detectable hygroscopic growth of GFG-soot and enhanced the activated fraction of GFG- (carrier gas: argon) and CAST-soot, whereas no hygroscopic growth of the coated CAST-soot was found. Sulfuric acid coatings led to an OC-content dependent hygroscopic growth of CAST-soot. Such a dependence was not observed for activation measurements. Coating with sulfuric acid decreased the amount of Polycyclic Aromatic Hydrocarbons (PAH), which were detected by AMS-measurements in the CAST-soot, and increased the amount of substances with lower molecular weight than the initial PAHs. We assume that these reaction products increased the hygroscopicity of the coated particles in addition to the coating substance itself.

In climate and weather models, the quantitative description of aerosol and cloud processes relies on simplified assumptions. This contributes major uncertainties to the prediction of global and regional climate change. Therefore, models need good parameterizations for heterogeneous ice nucleation by atmospheric aerosols. Here the authors present a new parameterization of immersion freezing on desert dust particles derived from a large number of experiments carried out at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber facility. The parameterization is valid in the temperature range between −12° and −36°C at or above water saturation and can be used in atmospheric models that include information about the dust surface area. The new parameterization was applied to calculate distribution maps of ice nuclei during a Saharan dust event based on model results from the regional-scale model Consortium for Small-Scale Modelling–Aerosols and Reactive Trace Gases (COSMO-ART). The results were then compared to measurements at the Taunus Observatory on Mount Kleiner Feldberg, Germany, and to three other parameterizations applied to the dust outbreak. The aerosol number concentration and surface area from the COSMO-ART model simulation were taken as input to different parameterizations. Although the surface area from the model agreed well with aerosol measurements during the dust event at Kleiner Feldberg, the ice nuclei (IN) number concentration calculated from the new surface-area-based parameterization was about a factor of 13 less than IN measurements during the same event. Systematic differences of more than a factor of 10 in the IN number concentration were also found among the different parameterizations. Uncertainties in the modeled and measured parameters probably both contribute to this discrepancy and should be addressed in future studies.

We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of aerosols from different emissions sources without limitation from the instruments or facilities available at any single site. The chamber can be mounted on a trailer for transport to host facilities or for mobile measurements. Photochemistry is simulated using a set of 40 UV lights (total power 4 KW). Characterisation of the emission spectrum of these lights shows that atmospheric photochemistry can be accurately simulated over a range of temperatures from −7–25 °C. A photolysis rate of NO2, JNO2, of (8.0 ± 0.7) × 10−3 molecules cm−3 s−1 was determined at 25 °C. Further, we present the first application of the mobile chamber and demonstrate its utility by quantifying primary organic aerosol (POA) emission and secondary organic aerosol (SOA) production from a Euro 5 light duty gasoline vehicle. Exhaust emissions were sampled during the New European Driving Cycle (NEDC), the standard driving cycle for European regulatory purposes, and injected into the chamber. The relative concentrations of oxides of nitrogen (NOx) and total hydrocarbon (THC) during the aging of emissions inside the chamber were controlled using an injection system developed as a part of the new mobile chamber set up. Total OA (POA + SOA) emission factors of (370 ± 18) × 10−3 g kg−1 fuel, or (14.6 ± 0.8) × 10−3 g km−1, after aging, were calculated from concentrations measured inside the smog chamber during two experiments. The average SOA/POA ratio for the two experiments was 15.1, a much larger increase than has previously been seen for diesel vehicles, where smog chamber studies have found SOA/POA ratios of 1.3–1.7. Due to this SOA formation, carbonaceous particulate matter (PM) emissions from a gasoline vehicle may approach those of a diesel vehicle of the same class. Furthermore, with the advent of emission controls requiring the use of diesel particle filters, gasoline vehicle emissions could become a far larger source of ambient PM than diesel vehicles. Therefore this large increase in the PM mass of gasoline vehicle aerosol emissions due to SOA formation has significant implications for our understanding of the contribution of on-road vehicles to ambient aerosols and merits further study.

The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.

During the eruption of the Eyjafjallajökull volcano in the south of Iceland in April/May 2010, about 40 Tg of ash mass were emitted into the atmosphere. It was unclear whether volcanic ash particles with d < 10 μm facilitate the glaciation of clouds. Thus, ice nucleation properties of volcanic ash particles were investigated in AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber experiments simulating atmospherically relevant conditions. The ash sample that was used for our experiments had been collected at a distance of 58 km from the Eyjafjallajökull during the eruption period in April 2010. The temperature range covered by our ice nucleation experiments extended from 219 to 264 K, and both ice nucleation via immersion freezing and deposition nucleation could be observed. Immersion freezing was first observed at 252 K, whereas the deposition nucleation onset lay at 242 K and RHice =126%. About 0.1% of the volcanic ash particles were active as immersion freezing nuclei at a temperature of 249 K. For deposition nucleation, an ice fraction of 0.1% was observed at around 233 K and RHice =116%. Taking ice-active surface site densities as a measure for the ice nucleation efficiency, volcanic ash particles are similarly efficient ice nuclei in immersion freezing mode (ns,imm ~ 109 m−2 at 247 K) compared to certain mineral dusts. For deposition nucleation, the observed ice-active surface site densities ns,dep were found to be 1011 m−2 at 224 K and RHice =116%. Thus, volcanic ash particles initiate deposition nucleation more efficiently than Asian and Saharan dust but appear to be poorer ice nuclei than ATD particles. Based on the experimental data, we have derived ice-active surface site densities as a function of temperature for immersion freezing and of relative humidity over ice and temperature for deposition nucleation.

The University of Toronto continuous flow diffusion chamber (UT-CFDC) was used to study heterogeneous ice nucleation at the International Workshop on Comparing Ice Nucleation Measuring Systems (ICIS 2007) which also represented the 4-th ice nucleation workshop, on 14–28 September 2007. One goal of the workshop was to inter-compare different ice nucleation measurement techniques using the same aerosol sample source and preparation method. The aerosol samples included four types of desert mineral dust, graphite soot particles, and live and dead bacterial cells (Snomax®). This paper focuses on the UT-CFDC results, with a comparison to techniques of established heritage including the Colorado State CFDC and the AIDA expansion chamber. Good agreement was found between the different instruments with a few specific differences, especially at low temperatures, perhaps due to the variation in how onset of ice formation is defined between the instruments and the different inherent residence times. It was found that when efficiency of ice formation is based on the lowest onset relative humidity, Snomax® particles were most efficient followed by the desert dusts and then soot. For all aerosols, deposition mode freezing was only observed for T

An ice nucleus counter was developed and constructed to enable investigation of potential ice nucleating materials. The Manchester Ice Nucleus Chamber (MINC) is a concentric-cylinder continuous flow diffusion chamber (CFDC). A full explanation of the MINC instrument is given here, along with first results and a comparison to an established instrument of similar design (Colorado State University CFDC) during sampling of common ice nucleating aerosols at the 2007 International workshop on Comparing Ice nucleation Measuring Systems (ICIS-2007). MINC and CSU-CFDC detected the onset of ice nucleation under similar conditions of temperature and supersaturation for several different types of ice nuclei. Comparisons of the ratio of ice nuclei to total aerosol concentrations as a function of supersaturation with respect to water (SSw) showed agreement within one order of magnitude. Possible reasons for differences between the two instruments relating to differences in their design are discussed, along with suggestions to future improvements to the current design.

Dust particles represent a dominant source of particulate matter (by mass) to the atmosphere, and their emission from some source regions has been shown to be transported on regional and hemispherical scales. Dust particles' potential to interact with water vapor in the atmosphere can lead to important radiative impacts on the climate system, both direct and indirect. We have investigated this interaction for several types of dust aerosol, collected from the Southwestern United States and the Saharan region. A continuous flow diffusion chamber was operated to measure the ice nucleation ability of the dust particles in the temperature range of relevance to cirrus and mixed-phase clouds (−65

Secondary organic aerosol (SOA) formation has been investigated as a function of temperature and humidity for the ozone-initiated reaction of the two monoterpenes α-pinene (243–313 K) and limonene (253–313 K) using the 84.5 m3 aerosol chamber AIDA. This paper gives an overview of the measurements done and presents parameters specifically useful for aerosol yield calculations. The ozonolysis reaction, selected oxidation products and subsequent aerosol formation were followed using several analytical techniques for both gas and condensed phase characterisation. The effective densities of the SOA were determined by comparing mass and volume size distributions to (1.25±0.10) g cm−3 for α-pinene and (1.3±0.2) g cm−3 for limonene. The detailed aerosol dynamics code COSIMA-SOA proved to be essential for a comprehensive evaluation of the experimental results and for providing parameterisations directly applicable within atmospheric models. The COSIMA-assisted analysis succeeded to reproduce the observed time evolutions of SOA total mass, number and size distributions by adjusting the following properties of two oxidation product proxies: individual yield parameters (αi), partitioning coefficients (Ki), vapour pressures (pi) and effective accommodation coefficients (γi). For these properties temperature dependences were derived and parameterised. Vapour pressures and partitioning coefficients followed classical Clausius – Clapeyron temperature dependences. From this relationship enthalpies of vaporisation were derived for the two more and less volatile product proxies of α-pinene: (59±8) kJ mol−1 and (24±9) kJ mol−1, and limonene: (55±14) kJ mol−1 and (25±12) kJ mol−1. The more volatile proxy components had a notably low enthalpy of vaporisation while the less volatile proxy components gave enthalpies of vaporisation comparable with those of typical products from α-pinene oxidation, e.g. pinonaldehyde and pinonic acid.

Complex refractive indices for supercooled sulfuric acid solution droplets in the mid-infrared spectral regime (wavenumber range 6000-800 cm -1 ) have been retrieved for acid concentrations ranging from 33 to 10 wt % H 2 SO 4 at temperatures between 235 and 230 K, from 36 to 15 wt % H 2 SO 4 at temperatures between 225 and 219 K, and from 37 to 20 wt % H 2 SO 4 at temperatures between 211 and 205 K. The optical constants were derived with a Mie inversion technique from measured H 2 SO 4 /H 2 O aerosol extinction spectra that were recorded during controlled expansion cooling experiments in the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. The new data sets cover a range of atmospherically relevant temperatures and compositions in the binary sulfuric acid/water system for which infrared refractive indices have not been published so far, namely, the regime when supercooled H 2 SO 4 /H 2 O solution droplets at T < 235 K are subjected to an environment that is supersaturated with respect to the ice phase. With increasing ice supersaturation, the H 2 SO 4 /H 2 O aerosol particles will continuously dilute by the uptake of water vapor from the gas phase until freezing of the solution droplets eventually occurs when the acid concentration has dropped below a critical, temperature-dependent threshold value. With the aid of the new measurements, the homogeneous freezing process of supercooled H 2 SO 4 /H 2 O solution droplets at cirrus temperatures can be quantitatively analyzed by means of Fourier transform infrared spectroscopy, thereby overcoming a major drawback from previous studies: the need to use complex refractive indices that were measured at temperatures well above 235 K to deduce the composition of the low-concentrated H 2 SO 4 /H 2 O aerosol particles. As in the case of the complex refractive indices for sulfuric acid solutions with acid concentrations greater than 37 wt % H 2 SO 4 , the new low-temperature optical constants for highly diluted droplets also reveal significant temperature-induced spectral variations in comparison with the refractive indices for higher temperatures, which are associated with a change in the equilibrium between sulfate and bisulfate ions.

The ageing process of an air mass over South-West Germany during 5 consecutive days has been examined. In-situ measurements of the visibility, aerosol size distributions, aerosol scattering coefficients and meteorological variables as relative humidity were measured during that situation. Additionally, we measured column aerosol properties, and PM10 mass concentrations of a nearby station of the local environmental protection agency were available. A distinct decrease in the visibility from 45 to 25 km, which was directly measured by two independent methods, a significant increase in PM10, and an increase in the aerosol optical thickness from 0.1 to 0.6 have been detected. The visibility decrease is associated with distinct changes in the aerosol number–size distribution. The number of particles with diameters larger than 300 nm increased considerably during the period, whereas smaller particles did not show such a clear trend. A comparison with meteorological ranges derived from nephelometer scattering coefficients using the Koschmieder formula and a humidity correction is presented. The quality of the nephelometer measurements is verified by a comparison with meteorological ranges calculated from scanning mobility particle sizer (SMPS)/aerodynamic particle sizer (APS) aerosol size distributions applying Mie theory. The calculated meteorological ranges are too high in comparison with the measured visibilities in the beginning, whereas this overestimation decreases at the end of the period when more relatively large particles were abundant. Our results demonstrate the general lack of representativeness of an in-situ measurement for a horizontally averaged parameter as the observed visibility. However, this representativeness was improved when the visibility decreased. In addition, a clear reciprocal behaviour of the visibility and the aerosol optical thickness has been found.

About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday1. Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres2,3. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles4, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth5,6, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer7,8,9,10. Although recent studies11,12,13 predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon2, and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory)2,14, has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown15 that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10−4.5 micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10−4.5 to 10−0.5 micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations., Nature, 533 (7604), ISSN:0028-0836, ISSN:1476-4687

The AIDA (Aerosol Interactions and Dynamics in the Atmosphere) aerosol and cloud chamber of Forschungszentrum Karlsruhe can be used to test the ice forming ability of aerosols. The AIDA chamber is extensively instrumented including pressure, temperature and humidity sensors, and optical particle counters. Expansion cooling using mechanical pumps leads to ice supersaturation conditions and possible ice formation. In order to describe the evolving chamber conditions during an expansion, a parcel model was modified to account for diabatic heat and moisture interactions with the chamber walls. Model results are shown for a series of expansions where the initial chamber temperature ranged from −20°C to −60°C and which used desert dust as ice forming nuclei. During each expansion, the initial formation of ice particles was clearly observed. For the colder expansions there were two clear ice nucleation episodes. In order to test the ability of the model to represent the changing chamber conditions and to give confidence in the observations of chamber temperature and humidity, and ice particle concentration and mean size, ice particles were simply added as a function of time so as to reproduce the observations of ice crystal concentration. The time interval and chamber conditions over which ice nucleation occurs is therefore accurately known, and enables the model to be used as a test bed for different representations of ice formation.

Cloud microphysical processes involving the ice phase in tropospheric clouds are among the major uncertainties in cloud formation, weather and General Circulation Models (GCMs). The simultaneous detection of aerosol particles, liquid droplets, and ice crystals, especially in the small cloud-particle size range below 50 μm, remains challenging in mixed phase, often unstable ice-water phase environments. The Cloud Aerosol Spectrometer with Polarisation (CASPOL) is an airborne instrument that has the ability to detect such small cloud particles and measure their effects on the backscatter polarisation state. Here we operate the versatile Cosmics-Leaving-OUtdoor-Droplets (CLOUD) chamber facility at the European Organisation for Nuclear Research (CERN) to produce controlled mixed phase and other clouds by adiabatic expansions in an ultraclean environment, and use the CASPOL to discriminate between different aerosols, water and ice particles. In this paper, optical property measurements of mixed phase clouds and viscous Secondary Organic Aerosol (SOA) are presented. We report observations of significant liquid – viscous SOA particle polarisation transitions under dry conditions using CASPOL. Cluster analysis techniques were subsequently used to classify different types of particles according to their polarisation ratios during phase transition. A classification map is presented for water droplets, organic aerosol (e.g., SOA and oxalic acid), crystalline substances such as ammonium sulphate, and volcanic ash. Finally, we discuss the benefits and limitations of this classification approach for atmospherically relevant concentration and mixtures with respect to the CLOUD 8–9 campaigns and its potential contribution to Tropical Troposphere Layer (TTL) analysis.

Deposition nucleation experiments with Arizona Test Dust (ATD) as a surrogate for mineral dusts were conducted at the AIDA cloud chamber at temperatures between 220 and 250 K. The influence of the aerosol size distribution and the cooling rate on the ice nucleation efficiencies was investigated. Ice nucleation active surface site (INAS) densities were calculated to quantify the ice nucleation efficiency as a function of temperature, humidity and the aerosol surface area concentration. Additionally, a contact angle parameterization according to classical nucleation theory was fitted to the experimental data in order to relate the ice nucleation efficiencies to contact angle distributions. From this study it can be concluded that the INAS density formulation is a very useful tool to describe the temperature- and humidity-dependent ice nucleation efficiency of ATD particles. Deposition nucleation on ATD particles can be described by a temperature- and relative-humidity-dependent INAS density function ns(T, Sice) with ns(xtherm) = 1.88 ×105 · exp(0.2659 · xtherm) [m−2] , (1) where the temperature- and saturation-dependent function xtherm is defined as xtherm = −(T−273.2)+(Sice−1) ×100, (2) with the saturation ratio with respect to ice Sice >1 and within a temperature range between 226 and 250 K. For lower temperatures, xtherm deviates from a linear behavior with temperature and relative humidity over ice. Also, two different approaches for describing the time dependence of deposition nucleation initiated by ATD particles are proposed. Box model estimates suggest that the time-dependent contribution is only relevant for small cooling rates and low number fractions of ice-active particles.

The large (7 m×4 m cylinder, 84 m3) AIDA (Aerosol Interactions and Dynamics in the Atmosphere) cloud chamber facility at Forschungszentrum, Karlsruhe, Germany was used to test the ice nucleating ability of two desert dust samples from the Sahara and Asia. Aerosol samples were lognormally distributed with a mode diameter of 0.4(±0.1) μm and geometric standard deviation of ~1.7(±0.2). At temperatures warmer than −40°C droplets were formed before ice crystals formed and there was generally no deposition nucleation observed. At temperatures colder than −40°C both dust samples exhibited dual nucleation events that were observed during the same expansion experiment. The primary nucleation event occurred at ice saturation ratios of 1.1 to 1.3 and is likely to be a deposition nucleation mode. The secondary nucleation event occurred at ice saturation ratios between 1.35 and 1.5. We cannot categorically determine whether this ice nucleation event is via a further deposition mode or a condensation mode, but the presence of some soluble material in the dust samples leads us to favour the latter process. The activated fractions of desert dust ranged from ~5–10% at −20°C to 20–40% at temperatures colder than −40°C. There was no obvious difference between the nucleation behaviour of the two dust samples.

The aerosol chamber AIDA (Aerosol Interactions and Dynamics in the Atmosphere) was used as a moderate expansion cloud chamber to investigate the effect of the organic carbon (OC) content on the ice nucleation properties of soot aerosol particles. Two different soot samples with OC contents of 16 % (CS16) and 40 % (CS40) where produced with the CAST (Combustion Aerosol Standard) burner operated at different air/fuel (propane) ratios. In dynamic expansion experiments with about 30 %/min increase of relative humidity with respect to ice, the CS16 sample started to nucleate ice crystals at an ice saturation ratio S in of 1.45 (at a temperature of 207 K). This value is very close to the ice saturation ratio of ice nucleation onset on carbon spark generator soot particles coated with a significant amount of sulphuric acid investigated in previous AIDA expansion experiments. A second experiment with CS40 soot performed at almost identical thermodynamic conditions showed ice nucleation onset to occur at S in between 1.5 and 1.7. The formation rate of ice crystals was at least two orders of magnitude less than for CS16 soot, even at ice saturation ratios up to values of 1.9, which is very close to water saturation at a temperature of 207 K. Therefore, increasing the amount of OC seems to significantly suppress the ice nucleation on flame soot particles. In contrast, similar expansion experiments with dry and untreated mineral dust particles (Arizona test dust) in the temperature range 194 to 241 K showed ice nucleation to occur at much lower ice saturation ratios of only 1.05 to 1.15.

In situ Fourier transform infrared (FTIR) extinction spectra of airborne alpha-NAD microparticles generated by two different methods were recorded in the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. The extinction spectrum of alpha-NAD crystals obtained by shock freezing of a HNO3/H2O gas mixture could be accurately reproduced using Mie theory with published refractive indices of alpha-NAD as input. In contrast, Mie theory proved to be inadequate to properly reproduce the infrared extinction spectrum of alpha-NAD crystals which were formed via homogeneous nucleation of supercooled HNO3/H2O solution droplets, evaporating slowly on a time scale of several hours at about 195 K. Much better agreement between measured and calculated extinction spectra was obtained by T-matrix calculations assuming oblate particles with aspect ratios greater than five. This indicates that strongly aspherical alpha-NAD crystals are obtained when supercooled nitric acid solution droplets freeze and grow slowly, a process which has been discussed as a potential pathway to the formation of crystalline polar stratospheric cloud (PSC) particles.

A Differential Mobility Particle Sizer (DMPS) system has been adapted and tested for reliable aerosol characterization at stratospheric pressures and temperatures in the AIDA aerosol chamber of Forschungszentrum Karlsruhe. To avoid partial or complete evaporation of volatile aerosol particles (e.g. solution droplets like sulfuric acid droplets), the DMA is operated at almost the same temperature and pressure as the AIDA aerosol vessel. In this study, we describe the experimental setup and technical modifications to the TSI standard DMA 3071 and CPC 3010 used for the DMPS system, discuss the results of low pressure Latex calibration and CPC counting efficiency measurements, and demonstrate the performance of the entire system in a case study with sulfuric acid aerosol.

The ozonolysis of � -pinene in a large aerosol chamber was usedto generate second ary organic aerosol (SOA) mass by homogeneous nucleation, or by heterogeneous nucleation, either on soot, or on (NH4)2SO4 seedaerosols. The rate of the � -pinene + ozone reaction andthe aerosol yieldof ∼19% are in goodagreement with literature data. The organic coating of soot particles leads to a compaction of the fractal agglomerates expressedby an increase in fractal d imension from 1.9 to 2.1 for Diesel soot, andfrom 2.0 to 2.3 for spark generated“Palas” soot. The d ielectric coating of the soot particles with SOA layers between 2 to 11 nm gives rise to a substantial enhancement of their single scattering albedo, from about 0.2 to 0.5, and increases the e+ective absorption coeCcients of both soot types by ca. 30%. The coating of both soot types increases the hygroscopic growth factors (HGF) to values close below the HGF measuredfor pure SOA material d=d0∼1:12 at 90% RH. ? 2003 Elsevier Ltd. All rights reserved.

The UV-VIS-NIR spectral optical properties of soot and soot containing aerosols were investigated in detail during the AIDA Soot Aerosol Campaign 1999. One aim of the campaign was a comprehensive comparison of the microphysical properties of Diesel and spark generator soot. The mass specific extinction cross section at λ=450 nm of Diesel soot is 10.6±0.5 m 2 g −1 which is almost a factor of two larger than the corresponding value of 5.7±0.3 m 2 g −1 measured for spark generator soot. Coagulation-induced particle growth does not affect the soot extinction cross section and has a weak influence on the scattering properties of the soot aggregates. Atmospheric processing of freshly emitted soot was simulated in mixing experiments. The formation of mixed Diesel soot and dry ammonium sulfate particles by coagulation has only a minor effect on the soot absorption cross section. The coating of spark generated soot with organic material results in a strong increase of the single scattering albedo. A significant increase of the absorption coefficient at λ=473 nm during the coating process can be attributed to an enhancement of the specific soot absorption cross section by more than 30%.

International audience; The homogeneous freezing of supercooled H2SO4/H2O solution droplets was investigated in the aerosol chamber AIDA (Aerosol Interactions and Dynamics in the Atmosphere) of Forschungszentrum Karlsruhe. 24 freezing experiments were performed at temperatures between 189 and 235 K with aerosol particles in the diameter range 0.05 to 1 µm. Individual experiments started at homogeneous temperatures and ice saturation ratios between 0.9 and 0.95. Cloud cooling rates up to -2.8 K min-1 were simulated dynamically in the chamber by expansion cooling using a mechanical pump. Depending on the cooling rate and starting temperature, freezing threshold relative humidities were exceeded after expansion time periods between about 1 and 10 min. The onset of ice formation was measured with three independent methods showing good agreement among each other. Ice saturation ratios measured at the onset of ice formation increased from about 1.4 at 231 K to about 1.75 at 189 K. The experimental data set including thermodynamic parameters as well as physical and chemical aerosol analysis provides a good basis for microphysical model applications.

Version finale révisée de : Amato, P., Joly, M., Schaupp, C., Attard, E., Möhler, O., Morris, C. E., Brunet, Y.., and Delort, A.-M.: Survival and ice nucleation activity of bacteria as aerosols in a cloud simulation chamber, Atmos. Chem. Phys. Discuss., 15, 4055-4082, doi:10.5194/acpd-15-4055-2015, 2015.; International audience; The residence time of bacterial cells in the atmosphere is predictable by numerical models. However, estimations of their aerial dispersion as living entities are limited by a lack of information concerning survival rates and behavior in relation to atmospheric water. Here we investigate the viability and ice nucleation (IN) activity of typical atmospheric ice nucleation active bacteria (Pseudomonas syringae and P. fluorescens) when airborne in a cloud simulation chamber (AIDA, Karlsruhe, Germany). Cell suspensions were sprayed into the chamber and aerosol samples were collected by impingement at designated times over a total duration of up to 18 h, and at some occasions after dissipation of a cloud formed by depressurization. Aerosol concentration was monitored simultaneously by online instruments. The cultivability of airborne cells decreased exponentially over time with a half-life time of 250 ± 30 min (about 3.5 to 4.5 h). In contrast, IN activity remained unchanged for several hours after aerosolization, demonstrating that IN activity was maintained after cell death. Interestingly, the relative abundance of IN active cells still airborne in the chamber was strongly decreased after cloud formation and dissipation. This illustrates the preferential precipitation of IN active cells by wet processes. Our results indicate that from 106 cells aerosolized from a surface, one would survive the average duration of its atmospheric journey estimated at 3.4 days. Statistically, this corresponds to the emission of 1 cell that achieves dissemination every ~ 33 min m−2 of cultivated crops fields, a strong source of airborne bacteria. Based on the observed survival rates, depending on wind speed, the trajectory endpoint could be situated several hundreds to thousands of kilometers from the emission source. These results should improve the representation of the aerial dissemination of bacteria in numeric models.

The loss of ozone on carbon soot aerosol was investigated in the temperature range 238–330 K for reaction times up to 72 h: 200 μg m−3 ozone in dry synthetic air is depleted with an initial reaction probability γ=1.2×10−6 at 296 K. The reaction probability decreases with a characteristic time τ of about 12 h (1/τ=k3=(2.3±0.6)×10−5 s−1) due to surface passivation. The reaction rate has a positive temperature dependence, and a complex negative dependence on the ozone concentration. A minimum set of four quasi-elementary reactions is required to model the observed concentration and time dependencies of the ozone loss rate: rapid destruction of one monolayer equivalent of ozone on pristine surface sites (SS): SS+O3→SSO+O2 (I), ozone-induced recovery of reactive sites: SSO+O3→SS+2O2 (or SS'+O2+CO2) (IIa,b), spontaneous recovery of reactive sites: SSO→SS'+CO, and spontaneous site passivation: SSO→SSp (III). The kinetic parameters γ 2ab , k 2c , and k3, which were determined in 11 independent experiments, lead to the following analytical expression for the effective reaction probability γeff which applies when the fast initial surface oxidation has reached a steady state: γ eff =[2γ 2ab +2.6×10 15 k 2c /([ O 3 ]〈c〉)] exp (−k 3 t). This equation is valid over a wide range of atmospheric conditions. It implies that ozone depletion on dry soot aerosol is negligible both in the troposphere and lower stratosphere.

The AquaVIT-1 Intercomparison of Atmospheric Water Vapor Measurement Techniques was conducted at the aerosol and cloud simulation chamber AIDA at the Karlsruhe Institute of Technology, Germany, in October 2007. The overall objective was to intercompare state-of-the-art and prototype atmospheric hygrometers with each other and with independent humidity standards under controlled conditions. This activity was conducted as a blind intercomparison with coordination by selected referees. The effort was motivated by persistent discrepancies found in atmospheric measurements involving multiple instruments operating on research aircraft and balloon platforms, particularly in the upper troposphere and lower stratosphere where water vapor reaches its lowest atmospheric values (less than 10 ppm). With the AIDA chamber volume of 84 m3, multiple instruments analyzed air with a common water vapor mixing ratio, either by extracting air into instrument flow systems, locating instruments inside the chamber, or sampling the chamber volume optically. The intercomparison was successfully conducted over 10 days during which pressure, temperature, and mixing ratio were systematically varied (50 to 500 hPa, 185 to 243 K, and 0.3 to 152 ppm). In the absence of an accepted reference instrument, the reference value was taken to be the ensemble mean of a core subset of the measurements. For these core instruments, the agreement between 10 and 150 ppm of water vapor is considered good with variation about the reference value of about ±10% (±1σ). In the region of most interest between 1 and 10 ppm, the core subset agreement is fair with variation about the reference value of ±20% (±1σ). The upper limit of precision was also derived for each instrument from the reported data. These results indicate that the core instruments, in general, have intrinsic skill to determine unknown water vapor mixing ratios with an accuracy of at least ±20%. The implication for atmospheric measurements is that the substantially larger differences observed during in-flight intercomparisons stem from other factors associated with the moving platforms or the non-laboratory environment. The success of AquaVIT-1 provides a template for future intercomparison efforts with water vapor or other species that are focused on improving the analytical quality of atmospheric measurements on moving platforms.

Based on laboratory studies it has been suggested that the most important atmospheric aerosol particles acting as ice nuclei for heterogeneous freezing of cloud droplets at temperatures above −15°C could be from biological sources. Here we present simulations with a regional atmospheric model to investigate their impact on mixed-phase clouds based on recent experimental studies with different biological ice nuclei.

In this paper, the effect of the morphological modification of aerosol particles with respect to heterogeneous ice nucleation is comprehensively investigated for laboratory-generated hematite particles as a model substrate for atmospheric dust particles. The surface-area-scaled ice nucleation efficiencies of monodisperse cubic hematite particles and milled hematite particles were measured with a series of expansion cooling experiments using the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud simulation chamber. Complementary offline characterization of physico-chemical properties of both hematite subsets were also carried out with scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS), and an electro-kinetic particle charge detector to further constrain droplet-freezing measurements of hematite particles. Additionally, an empirical parameterization derived from our laboratory measurements was implemented in the single-column version of the Community Atmospheric Model version 5 (CAM5) to investigate the model sensitivity in simulated ice crystal number concentration on different ice nucleation efficiencies. From an experimental perspective, our results show that the immersion mode ice nucleation efficiency of milled hematite particles is almost an order of magnitude higher at −35.2 °C < T < −33.5 °C than that of the cubic hematite particles, indicating a substantial effect of morphological irregularities on immersion mode freezing. Our modeling results similarly show that the increased droplet-freezing rates of milled hematite particles lead to about one order magnitude higher ice crystal number in the upper troposphere than cubic hematite particles. Overall, our results suggest that the surface irregularities and associated active sites lead to greater ice activation through droplet freezing.

Since 2003, the AIDA cloud chamber has been used for comprehensive series of ice nucleation experiments with a variety of different aerosols and in wide ranges of temperature, relative humidity and cooling rate. Ice nucleation onset and ice formation rates have been obtained as a function of aerosol parameters, ice supersaturation, temperature and cooling rate for homogeneous freezing of water droplets and solution particles, immersion freezing at and below water saturation, and deposition ice nucleation between ice and water saturation. The AIDA team has started a consistent and comprehensive re-analysis of the 10 year data set to provide a new set of parameters for formulating the ice formation in atmospheric models as function of aerosol properties, temperature and humidity. Here we present basic concepts and some selected results.

Atmospheric secondary organic aerosol (SOA) is likely to exist in a semi-solid or glassy state, particularly at low temperatures and humidities. Previously, it has been shown that glassy aqueous citric acid aerosol is able to nucleate ice heterogeneously under conditions relevant to cirrus in the tropical tropopause layer (TTL). In this study we test if glassy aerosol distributions with a range of chemical compositions heterogeneously nucleate ice under cirrus conditions. Three single component aqueous solution aerosols (raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA) and levoglucosan) and one multi component aqueous solution aerosol (raffinose mixed with five dicarboxylic acids and ammonium sulphate) were studied in both the liquid and glassy states at a large cloud simulation chamber. The investigated organic compounds have similar functionality to oxidised organic material found in atmospheric aerosol and have estimated temperature/humidity induced glass transition thresholds that fall within the range predicted for atmospheric SOA. A small fraction of aerosol particles of all compositions were found to nucleate ice heterogeneously in the deposition mode at temperatures relevant to the TTL (ns, of the aerosols tested here and also of glassy citric acid aerosol as a function of relative humidity with respect to ice (RHi). We also propose a parameterisation which can be used to estimate heterogeneous ice nucleation by glassy aerosol for use in cirrus cloud models up to ~220 K. Finally, we show that heterogeneous nucleation by glassy aerosol may compete with ice nucleation on mineral dust particles in mid-latitudes cirrus.

The ice nucleation potential of airborne glassy aqueous aerosol particles has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 247 and 216 K. Four different solutes were used as proxies for oxygenated organic matter found in the atmosphere: raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA), levoglucosan, and a multi-component mixture of raffinose with five dicarboxylic acids and ammonium sulphate. Similar to previous experiments with citric acid aerosols, all particles were found to nucleate ice heterogeneously before reaching the homogeneous freezing threshold provided that the freezing cycles were started well below the respective glass transition temperatures of the compounds; this is discussed in detail in a separate article. In this contribution, we identify a further mechanism by which glassy aerosols can promote ice nucleation below the homogeneous freezing limit. If the glassy aerosol particles are probed in freezing cycles started only a few degrees below their respective glass transition temperatures, they enter the liquid regime of the state diagram upon increasing relative humidity (moisture-induced glass-to-liquid transition) before being able to act as heterogeneous ice nuclei. Ice formation then only occurs by homogeneous freezing at elevated supersaturation levels. When ice forms the remaining solution freeze concentrates and re-vitrifies. If these ice cloud processed glassy aerosol particles are then probed in a second freezing cycle at the same temperature, they catalyse ice formation at a supersaturation threshold between 5 and 30% with respect to ice. By analogy with the enhanced ice nucleation ability of insoluble ice nuclei like mineral dusts after they nucleate ice once, we refer to this phenomenon as pre-activation. We propose a number of possible explanations for why glassy aerosol particles that have re-vitrified in contact with the ice crystals during the preceding homogeneous freezing cycle exhibit pre-activation: they may retain small ice embryos in pores, have footprints on their surface which match the ice lattice, or simply have a much greater surface area or different surface microstructure compared to the unprocessed glassy aerosol particles. Pre-activation must be considered for the correct interpretation of experimental results on the heterogeneous ice nucleation ability of glassy aerosol particles and may provide a mechanism of producing a population of extremely efficient ice nuclei in the upper troposphere.

The ice nucleation activities of five different Pseudomonas syringae, Pseudomonas viridiflava and Erwinia herbicola bacterial species and of Snomax™ were investigated in the temperature range between −5 and −15°C. Water suspensions of these bacteria were directly sprayed into the cloud chamber of the AIDA facility of Forschungszentrum Karlsruhe at a temperature of −5.7°C. At this temperature, about 1% of the Snomax™ cells induced immersion freezing of the spray droplets before the droplets evaporated in the cloud chamber. The living cells didn't induce any detectable immersion freezing in the spray droplets at −5.7°C. After evaporation of the spray droplets the bacterial cells remained as aerosol particles in the cloud chamber and were exposed to typical cloud formation conditions in experiments with expansion cooling to about −11°C. During these experiments, the bacterial cells first acted as cloud condensation nuclei to form cloud droplets. Then, only a minor fraction of the cells acted as heterogeneous ice nuclei either in the condensation or the immersion mode. The results indicate that the bacteria investigated in the present study are mainly ice active in the temperature range between −7 and −11°C with an ice nucleation (IN) active fraction of the order of 10−4. In agreement to previous literature results, the ice nucleation efficiency of Snomax™ cells was much larger with an IN active fraction of 0.2 at temperatures around −8°C.

In aerosol chamber experiments optical properties of resuspended mineral dust samples of defined size distributions were measured. Extinction coefficients (bext) and mass specific extinction cross sections (σext) were determined for Saharan dust samples from different locations. The results for σext were not very sensitive to the type of dust and varied at λ=550 nm between 3.3±0.4 m2 g−1 and 3.7±0.4 m2 g−1. The absorption coefficients (babs) and mass specific absorption cross sections (σabs) were determined with a novel multi-wavelength photo-acoustic absorption spectrometer (PAS). The single scattering albedo was close to 1 (0.98 to 0.99) at 532 nm and 1064 nm, but significantly lower (0.63 to 0.76) at 266 nm. Additionally the chemical and mineralogical composition of the dust samples were analysed with special regard to the iron oxide phases hematite and goethite. At λ=266 nm the mineral dust sample without any detectable iron oxides showed a significantly higher SSA compared to the sample with a hematite content of 0.6 wt-%.

The low temperature aerosol chamber AIDA was used to study the nucleation of nitric acid dihydrate (NAD) in super-cooled nitric acid aerosols under simulated stratospheric conditions in the temperature range 192 K–197 K. The nucleating solution droplets had median diameters between 225 and 290 nm and molar fractions of nitric acid between 0.26 and 0.28. Nucleation of solid particles was unambiguously observed in two out of three experiments during time periods of up to five hours. The newly formed crystals could be clearly distinguished from the remaining liquid droplets by their increasing size with an optical particle spectrometer. The solid particles could be unequivocally identified as strongly aspherical nitric acid dihydrate crystals (α-NAD) by in-situ FTIR-spectroscopy. From our experimental data set there is no indication of direct nucleation of NAT or a conversion of NAD into NAT while having saturation ratios with respect to NAT of about 20–26. The temporal evolutions of the NAD particle concentrations were used to derive individual nucleation rates for NAD. The measured volume nucleation rates ranged from 3.9×105 cm−3 s−1 at 195.8 K and XNA=0.27 to 1.9×107 cm−3 s−1 at 192.1 K and XNA=0.28. The corresponding hypothetical surface nucleation rates of 2×100 to 1×102 cm−2 s−1 are smaller than the parameterization of Tabazadeh et al. (2002) by factors between 25 and >103., Atmospheric Chemistry and Physics, 6 (10), ISSN:1680-7375, ISSN:1680-7367

Series of infrared extinction spectra of ice crystals were recorded in the 6000–800cm−1 wavenumber regime during expansion cooling experiments in the large aerosol and cloud chamber AIDA of Forschungszentrum Karlsruhe. Either supercooled sulphuric acid solution droplets or dry mineral dust particles were added as seed aerosols to initiate ice formation after having established ice supersaturated conditions inside the chamber. The various ice nucleation runs were conducted at temperatures between 237 and 195K, leading to median sizes of the nucleated ice particles of 1–15µm. The measured infrared spectra were fitted with reference spectra from T-matrix calculations to retrieve the number concentration as well as the number size distribution of the generated ice clouds. The precise evaluation of the time-dependent ice particle number concentrations, i.e., the rates of new ice particle formation, is of particular importance to quantitatively analyse the ice nucleation experiments in terms of nucleation rates and ice activation spectra. The ice particles were modelled as finite circular cylinders with aspect ratios ranging from 0.5 to 3.0. Benefiting from the comprehensive diagnostic tools for the characterisation of ice clouds which are available at the AIDA facility, the infrared retrieval results with regard to the ice particle number concentration could be compared to independent measurements with various optical particle counters. This provided a unique chance to quantitatively assess potential errors or solution ambiguities in the retrieval procedure which mainly originate from the difficulty to find an appropriate shape representation for the aspherical particle habits of the ice crystals. Based on these inter-comparisons, we demonstrate that there is no standard retrieval approach which can be routinely applied to all different experimental scenarios. In particular, the concept to account for the asphericity of the ice crystals, the a priori constraints which might be imposed on the unknown number size distribution of the ice crystals (like employing an analytical distribution function), and the wavenumber range which is included in the fitting algorithm should be carefully adjusted to each single retrieval problem.